Anthracene dye and process of making same.



1 UNlTED STATES PATENT OFF CE! OSOAR BALLY, OF MANNHEIM, GERMANY, ASSIGNOR TO BADISCHE ANILIN 85 SODA FABRIK, OE LUDWIGSHAFEN, GERMANY, A CORPORATION, OF

GERMANY.

ANTHRACENEDYEAND PROCESS OF MAKING SAME.

SPECIFICATION formingpart of Letters Patent No. 707,373, dated August 19, 1902.

Application filed July 2, 1901. $erial No. 66,897. (No specimens.)

To all whom it'may concern.-

' Be it known that I, OSCAR BALLY, doctor of philosophy and chemist, a citizen of the Swiss Republic, residing at Mannheim, in the Grand Duchy of Baden, Germany,have invented-new and useful Improvements in Coloring-Matter of the Anthracene Series and Process of Producing Same, of which the following is a specification.

It is known that certain derivatives of amido-anthraquinone on treatment with bromin or chlorin yield well-defined halogenized products which can be condensed with primary aromatic amins to form dyestufis.

I have now discovered that the above-men-r of the sulfo-acid of a primary aromatic amin under pressure, and it is often advantageous to and a salt of the alkaline earths or of the alkalies, which can remove any hydrochloric acid or hydrobromic acid formed during the reaction-4hr example, calcium acetate.

The following examples will serve to further illustrate the nature of my invention and a manner of carrying it into practical effect; but I do not confine myself to the details therein given. The parts are by weight.'

Example 1-C0ndensati0n o7 hatogenized amido-anthraqainone monosnlfo acid with sodium satfanilata-Suspend one (1) part of crude (alpha and beta) anilido-anthraquinone sulfo-acid (obtainable according to the specification of Letters Patent No. 656,081) in twenty (20) parts of water. Add at ordinary temperature twelve (12) parts of bromin,(corresponding to three molecular proportions of bromin,) and stir for twelve (12) hours. Isolate by the addition of common salt the halosalt the coloring-matter formed.

genized product formed. Heat together in an enameled autoclave two and a half (2%)parts of the halogenized product thus obtained, five (5) parts of crystallized sodium sulfanilate, (containing water of crystallization,) and ten (10) parts ofwater to a temperature of one hundred and eighty (180) .degreescen- ,tigrade, until no further dyestuff is formed,

which is indicated when the color of the melt does not increase in intensity. When this point is reached, dissolve the mass in water and precipitate by the addition of common It can be purified by redissolving in water and again precipitating with common salt.v

Examplev 2O'0ndcnsation of brom betaamido-anthraquinonc monosalfo acid with sodium sntfanilatc.Heat together in an enameled autoclave two and a half (2%) parts of brom beta amido anthraqninone monosulfo-acid, (such as can be prepared in accordance with the Example 2 of the specification of the application for English Letters Patent No. 5,459 of 1900 with the aid of two molecular proportions of bromin,)" five (5) parts of sodium sulfanilate, (containing water of crystallizatiom) and ten (10) partsof water at a temperature of two hundred (200) degrees centigrade until the color of the melt no longer increases in intensity. When this' stage is reached, workup the reaction product as set forth in the foregoing Example 1.

Example 3- Condensation of brain-amidoanthraqainone s-aZfo-acid and metanilic acid, with the aid of calcium acetate.-Heat together in an enameled autoclave two and a half (2%) parts of the crude mixture of bromalpha and brom-beta amido-anthraquinone monosulfo-acids, (such as mentioned in Example 7 of the specification of the application for English Letters Patent No. 5,459 of 1900,) five (5) parts of a paste of metanilicacid (containing eighty-five per cent. of real acid) and ten (10) parts of a twenty-per-cent solution of calcium acetate at a temperature of two hundred (200) degrees centigrade for eight (8) hours, or until the blue color of the melt no longer increases in intensity. Treat the melt when cold with one hundred (100) parts of alcohol and two and a half (2%) parts of concentrated hydrochloric acid. Collect by filtering the coloring-matter which separates out.

Example 4-Oondensati0n of crude tetrabrom-diamido-anthraqu'mone with salfam'lic acid.-l-leat together ten (10) parts of crude tetra-brom-diamido-authraquinone, seventy parts of sodium sulfanilate, three (3) parts of crystallized sodium acetate, and ninety parts of water under pressure at a temperature of two hundred (200) to two hundred and twenty (220) degrees centigrade until a test portion is completely soluble in water. Salt out the coloring-matter formed with common salt, press, and dry.

Heat together five (5) parts of crude tetrabrom di toluido anthraquinone, eight (8) parts of sodium sulfanilate, and twenty (20) parts of water in an autoclave at a temperature of about two hundred and thirty (230) degrees centigrade until the mass has become bright green. The coloring-matter so obtained is insoluble, but by treating it with fuming sulfuric acid and boric acid in the known manner it can be converted into a sulfonated coloring matter soluble in water which dyes unmordanted wool green-blue and chrome-mordanted wool blue-green.

In the following table Igive some of the Example o-O0nden s'atton of ietm-brom-dzproperties of some of the new colorlng-rnattolmclo-anthraqumone 102th sulfamlw ac2d. ters obtainable according to this invention:

Behavior of Solution in aqueous so- BehzWior to- Solution in con coldconcen- W001 s 1 n lution toward warm centrated sultrated sulg gg Condensation product from- 0 111 Ward causalcohol and furic acid furlc acid to e d with tic sodaand color of the per cent. of which boric chrome sodium carsolution. 2 acid has bonate. been added.

Sulfanilic acid (alpha and beta) Dirty bluc- Color hardly Fairly-soluble 'v'iolet-bluc. Somewhat Gray-green.

amido-anthraquinone monosulfogreen. altered. Exdull violetbluer than acid brornid (brominated with cess causesa blue. the soluthree molecularproportionsofbl'oprecipitate. tion in sulmiu.) Crude coloring-matter. furic acid alone.

Sulfanilic acid+ (alpha and beta) Bright blue- B ee 0 m e l airly-soluble Violet-blue Blue Bluishgiccn. amido-anthraquinone 1nouosulfo green. greener. Exgreen-blue. acid bromid (brominated with cess causcsa three molecular proportions of bro= precipitate. min.) Purified coloring-matter.

Sulfanilic acid (alpha and beta) Dull blu e- Dullens the Fairlysolublc Blue Blue Gray-groom anilido-authraquinone monosulfogreen. color of the blue. acid bromid (brolniuated with four aqueous somolecular proportions of bromin.) lution.

Sulfanilic acid +beta-aniido anthra- Violet Color hardly Rcd-violet Dull rcd-violet.. Dullblue-vio- Gray-blue.

quinone monosulfo acid bromid c h a 11 g ed. let.

(broniinated with two molecular Excess proproportions of bromin.) duces a precipitatc.

Sulfanilic acid+alpha-amido-an- Blue do Violet Dullcherry-red. Violet Gray-violet.

thraquinone nionosulfo-acid bromid (brominated with three molecular proportions of bromin.)

Sulfanilic acid (alpha and beta) Violet blue... Dullens th e Violet Cherry-red..." Violet Gray-blue.

amido-anthraquinone lnonosulfocolor of the acid bromid (brominated with four aqueous somolecular proportions of bromin.) lution.

Metanilic acid (alpha and beta) Violet. B e c o In e s Hardly solu- Violet-red Blueviolet... Gray-blueio amido-anthraquinone monosulfogreenerwith ble. blue-black. acid bromid (bromin ated with four caustic soda, molecular proportions of bromin.) but little altered with sodium carbonatc.

Sull'auilic acid crude tetra-brom- Brown-violet Unchanged... Insoluble..." Brown Hardly al- Brown-red diamido-authraquinone. tered.

Sulfo-acidef the condensation prod- Bluegreen B e c o m e s DilTic-ultly sol- Blue-green Yellow-green. Bluishg'rccn.

not from sulfanilic acid+ crude greenerwith uble with tetrabrom-l.E-di-para-toluido-ancaustic soda. blue color. thraquiuone. Un c hanged with sodium carbonate.

Now what I claim is 1. The process of manufacturing coloringmatters by condensing halogenized amideanthraquinone substances with the sulfoacids of primary aromatic amins.

2. The process of manufacturing coloringmatters by condensing halogenized amidoanthraquinone substances with the sulfoacids of primary aromatic amine and sulfonating the products thus obtained.

3. The new coloring-matters such as can be obtained by condensing halogenized amidoanthraquinone substances with the sulfoacids of primary aromatic amins, and sulfonating if increased solubility in water is desired, and which are characterized by the following properties: soluble in water giving a, In testimony whereof I have hereunto set blue-green to violet solution; soluble in conmy hand in the presence of two subscribing oentrated sulfuric acid in the presence of witnesses.

boric acid giving greenish to bluish or violet OSCAR BALLY. 5 solutions; soluble in concentrated sulfuric Witnesses:

acid alone giving reddish to bluish or violet JOHN L. I-IEINKE,

colored solutions. JACOB ADRIAN. 

